Quantitative Inorganic Analysis Laboratory

Formal Report
Date Performed: 16-21
October 2015
Date Submitted: 22
October 2015
Department of Mining,
Metallurgical and
Materials Engineering
College of Engineering
Instructor: Searle
Aichelle Duay
Quantitative Determination of Dissolved
Oxygen Content by Winkler Redox Titration
D.A. Mercado
The dissolved oxygen content in a water sample collected from a pond in the
University was analyzed through Winkler redox titration. The water sample obtained
was treated with several reagents which lead to the production of Mn 2O3 precipitate.
This was then reacted with acid, dissolving the precipitate, thus producing iodide which
was titrated with thiosulfate. It was found that the DO content of the water sample was
8.00 ppm O 2 and according to the water guidelines of American Public Health
Association, Inc. the water sample is clean and good water. It is recommended that the
biological oxygen demand also be analyzed in order to take into account the effect of
time and temperature on the oxygen concentration. [2] If a dissolved oxygen sensor is
made available, it would be best to use this in order to produce more accurate results.

Introduction
Dissolved oxygen content, also denoted as DO,
plays a pertinent role in environmental and marine
science. It can be used to study the water masses in the
ocean, be a means of measuring the redox potential of
the water column and more importantly test the water
for pollution and its ability to support living things. In
order to accurately measure the concentration of the
dissolved oxygen, a process developed by Winkler in
1888 called the Winkler Redox Titration is used. [1]
The Winkler Redox Titration, an iodometric
process, is based off on the quantitative oxidation of
manganese (II) due to the presence of oxygen which
then leads to the production of manganese (III). Iodine
is then released due to the addition of the acid, which
can then be related to the dissolve oxygen content in
the water sample through its titration with thiosulfate
since oxygen has a 1:4 ratio with S 2O32-. [2] This
experiment aims to use the Winkler Redox titration
method in order to determine the amount of dissolved
oxygen in a water sample as well as perform the
necessary pre-treatment techniques in order to properly
assess the quality of the water obtained from the pond
in the University.
Materials and Methods
The 0.0125 M Sodium Thiosulfate solution was
standardized by placing 0.1499g of the KIO3 primary
standard in a 50 mL beaker. It was then dissolved using
50 mL distilled water and was diluted to mark in a 100
mL volumetric flask. Three 10.00 mL aliquots were then
taken from the diluted solution then were transferred into
separate 250 mL Erlenmeyer flasks. Then 20 mL distilled
Quantitative Determination of Dissolved Oxygen Content by Winkler Redox Titration
water was added into each flask followed by 1.0g KI and
10 mL of 0.5 M H2SO4. The solutions were then titrated
immediately with the Na2S2O3 standard until a pale
yellow color was observed. One milliliter of the starch
solution was immediately added then the titration process
was continued until the blue color disappeared.
The water sample to be analyzed was collected from
a pond in the University by taking a glass bottle that has
been covered with aluminum foil and filling it to the brim
with the sample, taking note to exclude any air bubbles.
The cover was then removed slowly and the following
reagents were then added in order, using a syringe: 0.5
mL of 4.0 M MnSO4 solution, 0.5 mL of 4.8 M
NH4HCO3 solution and 0.5 mL of 18.0 M NaOH with KI
and NaN3 solution. In order to avoid the inclusion of air
bubbles, the tip of the syringe was just below the surface
of the water sample. The bottle was then carefully closed
then vigorously shaken, thus creating a solution filled
with precipitates. The cover of the bottle was slowly
removed then 2.0 mL of concentrated H 3PO4 was added
into the solution, dissolving the precipitates. The bottle
was covered and shaken for a second time and was let to
stand in a dark atmosphere for 10 minutes. If the
resulting solution was dark yellow, an aliquot of 50 mL
was taken from it and was then transferred into a 250 mL
Erlenmeyer flask. In the case of a pale yellow solution,
100 mL of the sample was taken. Then just like in the
standardization process, the solution was titrated with the
Na2S2O3 standard until a pale yellow color was observed,
followed by the addition of the starch solution (1 mL).
The titration of the solution was the continued until the
blue color disappeared.
Results and Discussion
Mercado, 2015| 1
 In this experiment the Winkler redox titration was titrated with the 0.0073206 M thiosulfate,

where in the
done by using the titrant Na 2S2O3. It was standardize with iodine formed will revert back to I just as in equation
the KIO3 primary standard. To this, H 2SO4 and KI were 2. If a dark yellow color is obtained this means that the
added since these arecomponents that are needed in iodine concentration in the solution is still very high,
order to produce the I3 needed in equation 2. which is why it needs to be titrated with the thiosulfate

first until the desired pale yellow color is obtained before
IO3 + 8I + 6H 3I3 + 3H2O the starch solution is added.
2
(1)
2S2O3 + I3 S4O6 + 3I A starch indicator, a widely used indicator in redox
(2) reactions involving iodide, is used as the indicator in this
analysis since starch forms a blue complex with the
This standardization step gave the average molarity of triiodide ion. As the thiosulfate is added into this
Na2S2O3 to be 0.0073206 M. This was then used to titrate solution, which acts as the reducing agent, the iodide ion
the water sample that was collected from pond by the concentration will be higher than that of the iodine ion
Math building in the University. In order to prepare the thus removing the blue color of the solution. The change
water sample for titration, MnSO 4 was first added into the of color from blue to colorless indicates the endpoint of
bottle to introduce the Mn2+ ions into the solution. The the solution as the iodine changes to iodide, which is
presence of manganese is very important since the seen in equation 2. [3] It is important that the starch
method being used is based on its oxidation. The next indicator is added towards the end of the titration when
reagent added into the solution was the NH4HCO3 which the solution turns a pale yellow. If it is added too early,
changed the manganese ions into carbonates which are the high concentrations of iodine will react with the
sensitive to oxygen and thus eradicates the influence of starch thus forming an iodine-starch complex. The
other dissolved organic compounds.
2
The addition of endpoint of the solution will be indeterminate since the
NaOH
then causes the Mn ions to bind with the free excess iodine in the complex formed will dissociate
OH thus forming Mn(OH)2. Due to the presence of slowly.
dissolve oxygen, the previously formed Mn(OH) 2 will be
oxidized and form a precipitate of either Mn(OH) 3 or As the endpoint was reached as the blue color of the
MnO(OH) as seen in equation 5 and 6. Phosphoric acid is solution disappeared, the net volume of the Na 2S2O3
then added to the solution which dissolves the precipitate
2
needed for each trial was taken to be 8.7 mL, 6.1 mL and
that was formed since it is acidified, producing Mn . 5.7 mL, respectively. The dissolved oxygen content was
The excess iodide will thenbe oxidize forming I 2 which then calculated by using the relationship of the moles of
will react with the excess I produced

by the addition of O2 and S2O32- (1 mmol O2 = 4 mmol S2O32-), which gave
KI creating the iodine complex I 3 . The addition of the an average DO content of 8.00 ppm O2.
reagents must be in the said sequence to guarantee that
the iodine complex is formed. Any mix ups in the order Table 1. Water Quality Guidelines
may produce products that may interfere with the DO Content Water Quality
titration process and yield inaccurate results due to the (ppm O2) 20C
impurities formed. 8-9 Clean, good 7 11 ppm: ideal for
2 water stream fishes
MnSO4 + I3 Mn + SO4 6.7 7.9 Slightly including cold water
2
(3)
polluted fishes
Mn + 2OH Mn(OH)2 (4)
O2 + 4Mn(OH)2 + 2H2O 4Mn(OH)3 (s) (5) 4.5 6.6 Moderately polluted, can sustain life
O2 + 4Mn(OH)2 4MnO(OH)
(s) + 2H2O (6) of warm water fishes
I2 +I
I 3
2
(7) Below 4.5 Highly polluted
2Mn(OH)3 (s) + 6H + 2I 2Mn + I2 + 6H2O 0-2 Cannot sustain life
(8) 2
MnO(OH)(s) + 6H + 2I 2Mn + I2 + 4H2O The calculated DO content of the water sample is
(9) then compared to the water quality guidelines given by
American Public Health Association, Inc. which shows
Before this solution is titrated it is allowed to stand that at 8.00 ppm O2 the water collected from the pond by
in a dark atmosphere for 10 minutes in order to allow the the Math building in the University is clean and good
solution to go into completion and to prevent the increase water and thus can sustain aquatic life and is ideal for
in the rate of decomposition of the acid due to the cold water fishes. In comparison with the results obtained
presence of light. A pale yellow color is expected to be by the other groups analyzing the water sample from the
obtained to which the starch solution is added and is then same area, it can be seen that the average DO content is
Quantitative Determination of Dissolved Oxygen Content by Winkler Redox Titration Mercado, 2015| 2
near the average of the entire data set which shows that also takes note of the biochemical oxygen demand and
the data obtained was accurate and precise, with the can be used for long- term monitoring. Another method
statistical parameters given in Table 2. that can be used is the colorimetric method, which like
the Winkler method is fast to use and is inexpensive. The
colorimetric method has to variations called the indigo
carmine method and the rhodazine D method. In these
Table 2. Statistical Parameters in relation with other methods, the reagent is oxidized and the change in color
data sets is used as a measure of the dissolved oxygen content. [6]
Statistical Parameter Calculated Value References
Range 12.53
Relative Standard 368.11 ppt [1] Massachusetts Institute of Technology.
Deviation (ppt) Determination of Dissolved Oxygen by Winkler
Confidence Limits 8.43 2 Titration. http://ocw.mit.edu/courses/earth-atmospheric-
(95% confidence level) and-planetary-sciences/12-097-chemical-investigations-of-
Pooled Standard 3.10223 boston-harbor-january-iap-2006/labs/dissolved_
Deviation oxygen.pdf. (accessed 17 October 2015).

The possible source of error in this experiment could [2] University of Canterbury. http://www.outreach.
come from the collection and treatment of the water canterbury.ac.nz/chemistry/documents/dissolved_oxygen.
sample. If air bubbles are included in the sample, the pdf. (accessed 18 October 2015).
calculated dissolved oxygen content would be higher
than its actual value. This can be avoided by making sure [3] Skoog, D.; West, D.; Holler, F.J.; Crouch, S.
that the tip of the pipette or syringe is just below the Fundamentals of Analytical Chemistry,9th ed.; Cengage
surface of the water when adding the reagents. If the Learning Asia Pte Ltd: Singapore, 2014; pp 495.
sequence of the addition of the reagents in the treatment
process were not followed, this would result to the [4] Frostburg State University.
production of unnecessary products, whose presence has http://antoine.frostburg
an indeterminate effect on the calculated DO. The .edu/chem/senese/101/redox/faq/iodometry-iodimetry
addition of the reagents should also be done quickly .html (accessed 19 October 2015).
because if the intervals between the addition of each
reagent is too long, unwanted reactions may occur thus
becoming a source of error. The order of the addition of [5] Cary Institute of Ecosystem Studies. http://www.
the sulfuric acid and KI crystals must be followed caryinstitute.org/educators/teaching-materials/changing
because if the acid were added into the solution before -hudson-project/ecosystems-action-cycling-matter-
the KI crystals, it would favor the formation of HIO 3 energy/oxyge-3. (accessed 19 October 2015).
instead of the I3 that is needed which would result to a
decrease in I2 and calculated DO as well. [6] Kemker, Christine. Measuring Dissolved Oxygen.
Fundamentals of Environmental Measurements.
Conclusions and Recommendations Fondriest Environmental, Inc. 7 Jan.
2014.http://www.fondriest.com/environmental-measure
The dissolve oxygen content of the water sample ments/equipment/measuring-water-quality /dissolved-
collected from the pond by the Math building in the oxygen-sensors-and-methods/.(accessed 19 October
University was found to be 8.00 ppm O 2. This shows that 2015)
the water is clean and good and that it can sustain aquatic
life such as cold water fishes. It would be recommended
to obtain the biochemical oxygen demand of the water as
well in order to further assess the quality of the water
sample. There are several different ways to measure the
dissolve oxygen content in a water sample, other than the
Winkler redox titration process. One of which is by using
an electrochemical or optical sensor. This method may be
expensive and not widely available but it is the most
effective and accurate method since it eliminates human
error as well as errors caused by the presence of other
redoxing agents found in the water sample. This method
Quantitative Determination of Dissolved Oxygen Content by Winkler Redox Titration Mercado, 2015| 3
 Appendix I

Table I. Standardization of Na2S2O3 solution

Trial 1 KIO3 Weight [g] Net Volume Na2S2O3 [mL]

1 0.1499 56.7
2 0.1540 58.5
3 0.1500 57.6

Table II. Sample Analysis

Trial Net Volume Na2S2O3 [mL]

1 8.7
2 6.1
3 5.7
Location of Sampling Math Building
Total Volume of Sample 50 mL

Table III. Reported Values

Trial Molarity [M] DO Content [ppm O2]

1 0.007368 10.19
2 0.007336 7.14
3 0.007258 6.68
Average 0.0073206 8.00

Calculations
Molarity Na2S2O3
1molKIO3 6molNa2 S 2 O3 10
(0.1499 gKIO3 ) (0.994)
214.001g 1molKIO3 100
Trial 1: = 0.007367843 M Na2S2O3
56.7 mL
1000
1molKIO3 6molNa2 S 2 O3 10
(0.1540 gKIO3 ) (0.994)
214.001g 1molKIO 100
Trial 2: 3 = 0.007336462 M Na2S2O3
58.5mL
1000
1molKIO3 6molNa2 S 2 O3 10
(0.1500 gKIO3 ) (0.994)
214.001g 1molKIO3 100
Trial 3: = 0.007257559 M Na2S2O3
57.6mL
1000
(0.007367843) (0.007336462) (0.007257559)
Average: = 0.0073206 M Na2S2O3
3

Quantitative Determination of Dissolved Oxygen Content by Winkler Redox Titration Mercado, 2015 | 4
DO Content
1mmolO2 32mgO2
(0.0073206M )(8.7mL )
4mmolS 2 O32 1mmolO2
Trial 1: = 10.19 ppm O2
50mL
1000
1mmolO2 32mgO2
(0.0073206M )(6.1mL )
4mmolS 2 O32 1mmolO2
Trial 2: = 7.14 ppm O2
50mL
1000
1mmolO2 32mgO2
(0.0073206M )(5.7mL )
2

4 mmolS O
2 3 1mmolO 2 = 6.68 ppm O
Trial 3: 2
50mL
1000
(10.19) (7.14) (6.68)
Average: = 8.00 ppm O2
3
Statistical Parameters
Range: 17.33 4.8 = 12.53
Relative Standard Deviation
s 3.102239979
RSD = x 1000 ppt = x 1000 = 368.11 ppt
X 8.427391304
Confidence Limit
ts (3.119)(3.102239979)
CL = X = 8.43 = 8.43 2
n 23
Pooled Standard Deviation
n1 n2 n3

Spooled =
( X i X1 )2 ( X j X 2 )2 ( X k X 3 )2
i 1 j 1 k 1 = 3.10223
n1 n2 n3 ... ns

Quantitative Determination of Dissolved Oxygen Content by Winkler Redox Titration Mercado, 2015 | 5
 Appendix II
Answers to Questions:

1. How is the analysis (an iodometric process) different from an iodimetric one?
In the experiment, the analyte used was the oxidizing agent to which the excess iodide was added in order to
produce iodine. This is then titrated with sodium thiosulfate in order to determine the iodine produced. This process is
commonly called iodometry. An iodimetric process on the other hand uses an analyte that is a reducing agent which is
then titrated with a standard iodine solution. [4]
2. Predict the effect, if any, of each of the following on the DO oxygen content obtained:
a. The water sample is made to stand overnight before analysis.
The water sample may contain oxygen consuming microorganisms, some of which may undergo cellular
respiration, thus decreasing the amount of oxygen in the sample. The other microorganisms present on the other hand
may go through photosynthesis therefore producing more oxygen. As the temperature changes throughout the day, the
amount of dissolved oxygen in the water sample changes as well. As the temperature decreases, the amount of dissolved
oxygen increases. [5] With all of these factors combined, the effect on the dissolved oxygen content is indeterminate.

b. MnSO4 is added and the solution made to stand for an hour before the alkaline KI solution is added.
The manganese ions will react with the oxygen in the solution, thus forming MnO. Since the compound is
insoluble in water, the calculated dissolved oxygen content will decrease.

Quantitative Determination of Dissolved Oxygen Content by Winkler Redox Titration Mercado, 2015 | 6
Quantitative Determination of Dissolved Oxygen Content by Winkler Redox Titration Mercado, 2015 | 7